Permeability of a Seemingly Nonporous Crystal Formed by a Discrete Metallocyclic Complex

We describe the structure and permeability of a crystalline material that appears to be nonporous in a conventional sense. The material is initially formed as a solvate, and removal of the solvent molecules under relatively mild conditions proceeds via a single-crystal to single-crystal transformation, leaving the host structure intact. Although discrete unoccupied voids of 108 Å3 are present in the structure, it is not possible to map open channels that represent an intuitive pathway for guest diffusion. Despite the apparent absence of pores, the material is permeable to a variety of gases including H2, O2, N2, CO, CH4, CO2, and I2. These findings show that porosity in crystalline systems cannot always be rationalized by considering the static structures and that as-yet unknown dynamic and cooperative mechanisms prevail by which porosity can be induced.